U.S. patent application number 15/574569 was filed with the patent office on 2018-05-31 for process for the production of biodegradable hydrocarbon fluids.
This patent application is currently assigned to TOTAL MARKETING SERVICES. The applicant listed for this patent is TOTAL MARKETING SERVICES. Invention is credited to Clarisse DOUCET, Laurent GERMANAUD.
Application Number | 20180148656 15/574569 |
Document ID | / |
Family ID | 53188951 |
Filed Date | 2018-05-31 |
United States Patent
Application |
20180148656 |
Kind Code |
A1 |
GERMANAUD; Laurent ; et
al. |
May 31, 2018 |
PROCESS FOR THE PRODUCTION OF BIODEGRADABLE HYDROCARBON FLUIDS
Abstract
The invention provides for a process for preparing a fluid
having a boiling point in the range of from 100 to 400.degree. C.
and comprising more than 95% isoparaffins and containing less than
100 ppm aromatic, comprising the step of catalytically
hydrogenating a feed comprising more than 95% by weight of a
hydrodeoxygenated isomerized hydrocarbon biomass feedstock, at a
temperature from 80 to 180.degree. C. and at a pressure from 50 to
60 bars. The invention also provides for a fluid having a boiling
point in the range of from 100 to 400.degree. C. and a boiling
range below 80.degree. C., said fluid comprising more than 95%
isoparaffins and less than 3% of naphthens by weight and having a
ratio of iso-paraffins to n-paraffins of at least 12:1, a
biodegradability at 28 days of at least 60%, as measured according
to the OECD 306 standard, a biocarbon content of at least 95% by
weight, containing less than 100 ppm aromatics by weight, and
comprising carbon expressed as CH3 sat less than 30%.
Inventors: |
GERMANAUD; Laurent;
(Heyrieux, FR) ; DOUCET; Clarisse; (Levallois
Perret, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TOTAL MARKETING SERVICES |
Puteaux |
|
FR |
|
|
Assignee: |
TOTAL MARKETING SERVICES
Puteaux
FR
|
Family ID: |
53188951 |
Appl. No.: |
15/574569 |
Filed: |
May 20, 2016 |
PCT Filed: |
May 20, 2016 |
PCT NO: |
PCT/EP2016/061504 |
371 Date: |
November 16, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 45/44 20130101;
C10G 65/043 20130101; C10G 2300/1011 20130101; Y02P 30/20 20151101;
C10L 1/04 20130101; C10G 45/02 20130101; C10G 3/50 20130101; C10G
45/60 20130101; C10G 65/08 20130101; C10G 65/04 20130101; C10G
2300/301 20130101; C10G 45/58 20130101; C10G 3/42 20130101 |
International
Class: |
C10G 45/60 20060101
C10G045/60 |
Foreign Application Data
Date |
Code |
Application Number |
May 20, 2015 |
EP |
15168546.8 |
Claims
1. Process for preparing a fluid having a boiling point in the
range of from 100 to 400.degree. C. and comprising more than 95%
isoparaffins and containing less than 100 ppm aromatic by weight,
comprising the step of catalytically hydrogenating a feed
comprising more than 95% by weight of a hydrodeoxygenated
isomerized hydrocarbon biomass feedstock, at a temperature from 80
to 180.degree. C., at a pressure from 50 to 160 bars, a liquid
hourly space velocity of 0.2 to 5 h.sup.1 and an hydrogen treat
rate up to 200 Nm.sup.3/ton of feed.
2. Process of claim 1, wherein the hydrogenation conditions are the
following: Pressure: 80 to 150 bars, and preferably 90 to 120 bars;
Temperature: 120 to 160.degree. C. and preferably 150 to
160.degree. C.; Liquid hourly space velocity (LHSV): 0.4 to 3, and
preferably 0.5 to 0.8; Hydrogen treat rate be up to 200
Nm.sup.3/ton of feed.
3. Process of claim 1, wherein the feed comprises more than 98%,
preferably more than 99% of a hydrodeoxygenated isomerized
hydrocarbon biomass feedstock, and more preferably consists of a
hydrodeoxygenated isomerized hydrocarbon biomass feedstock.
4. Process of claim 1, wherein the biomass is a vegetable oil, an
ester thereof or a triglyceride thereof and advantageously the feed
is a NEXBTL feed.
5. Process of claim 1, wherein (i) a fractionating step is carried
out before the hydrogenating step, or after the hydrogenating step
or both, or (ii) the process comprises three hydrogenation stages,
preferably in three separate reactors, or (iii) both (i) and
(ii).
6. Process of claim 1, wherein the fluid has a boiling point in the
range 150 to 400.degree. C., preferably from 200 to 400.degree. C.,
especially 220 to 340.degree. C. and advantageously more than
250.degree. C. and up to 340.degree. C., and/or has a boiling range
below 80.degree. C., preferably below 60.degree. C., advantageously
between 40 and 50.degree. C.
7. Process of claim 1, wherein the fluid contains less than 50 ppm
aromatics by weight, preferably less than 20 ppm by weight.
8. Process of claim 1, wherein the fluid contains less than 3% by
weight of naphthens, preferably less than 1% and advantageously
less than 50 ppm by weight.
9. Process of claim 1, wherein the fluid comprises more than 98%
isoparaffins by weight.
10. Process of claim 1, wherein the fluid has a ratio of
iso-paraffins to n-paraffins of at least 12:1, preferably at least
15:1, more preferably at least 20:1.
11. Process of claim 1, wherein the fluid comprises more than 95%
by weight, of molecules with from 14 to 18 carbon atoms as
isoparaffins, preferably comprises by weight, from 60 to 95%, more
preferably 80 to 98%, of isoparaffins selected from the group
consisting of C15 isoparaffins, C16 isoparaffins, C17 isoparaffins,
C18 isoparaffins and mixtures of two or more thereof.
12. Process of claim 1, wherein the fluid comprises: C15
isoparaffins and C16 isoparaffins in a combined amount of 80 to
98%; or C16 isoparaffins, C17 isoparaffins and C18 isoparaffins in
a combined amount of 80 to 98%; or C 17 isoparaffins and C 18
isoparaffins in a combined amount of 80 to 98%.
13. Process of claim 1, wherein the fluid exhibits one or more,
preferably all of the following features: the fluid comprises
carbon expressed as Cquat less than 3%, preferably less than 1% and
more preferably about 0%; the fluid comprises carbon expressed as
CH sat less than 20%, preferably less than 18% and more preferably
less than 15%; the fluid comprises carbon expressed as CH.sub.2 sat
more than 40%, preferably more than 50% and more preferably more
than 60%; the fluid comprises carbon expressed as CH.sub.3 sat less
than 30%, preferably less than 28% and more preferably less than
25%; the fluid comprises carbon expressed as CH.sub.3 long chain
less than 20%, preferably less than 18% and more preferably less
than 15%; the fluid comprises carbon expressed as CH.sub.3 short
chain less than 15%, preferably less than 10% and more preferably
less than 9%.
14. Process of claim 1, wherein the fluid has a biodegradability at
28 days of at least 60%, preferably at least 70%, more preferably
at least 75% and advantageously at least 80%, as measured according
to the OECD 306 standard.
15. Process of claim 1, wherein the fluid has a biocarbon content
of at least 95%, preferably at least 97%, more preferably at least
98%, and even more preferably about 100%.
16. Fluid having a boiling point in the range of from 100 to
400.degree. C. and a boiling range below 80.degree. C., said fluid
comprising more than 95% isoparaffins and less than 3% of naphthens
by weight and having a ratio of iso-paraffins to n-paraffins of at
least 12:1, a biodegradability at 28 days of at least 60%, as
measured according to the OECD 306 standard, a biocarbon content of
at least 95% by weight, containing less than 100 ppm aromatics by
weight, and comprising carbon expressed as CH.sub.3 sat less than
30%.
17. Fluid according to claim 16, wherein at least one of the
following is true: the fluid has a boiling point in the range 150
to 400.degree. C.; the fluid contains less than 50 ppm aromatics by
weight; the fluid contains less than 3% by weight of naphthens; the
fluid comprises more than 98% isoparaffins by weight; the fluid has
a ratio of iso-paraffins to n-paraffins of at least 12:1; the fluid
comprises more than 95% by weight, of molecules with from 14 to 18
carbon atoms as isoparaffins; the fluid comprises C15 isoparaffins
and C16 isoparaffins in a combined amount of 80 to 98%; the fluid
comprises C16 isoparaffins, C17 isoparaffins and C18 isoparaffins
in a combined amount of 80 to 98%; the fluid comprises C 17
isoparaffins and C 18 isoparaffins in a combined amount of 80 to
98%; the fluid comprises carbon expressed as Cquat less than 3%;
the fluid comprises carbon expressed as CH sat less than 20%; the
fluid comprises carbon expressed as CH.sub.2 sat more than 40%; the
fluid comprises carbon expressed as CH.sub.3 sat less than 30%; the
fluid comprises carbon expressed as CH.sub.3 long chain less than
20%; the fluid comprises carbon expressed as CH.sub.3 short chain
less than 15%; the fluid has a biodegradability at 28 days of at
least 60%; or the fluid has a biocarbon content of at least 95%.
Description
FIELD OF THE INVENTION
[0001] The invention relates to the production of biodegradable
hydrocarbon fluids, hereinafter referred to as being improved
fluids, having a narrow boiling range and having a very low
aromatic content and their uses. The invention relates to a process
for producing these improved fluids by hydrogenation of HDO/ISO
feedstocks.
BACKGROUND ART
[0002] Hydrocarbon fluids find widespread use as solvents such as
in adhesives, cleaning fluids, solvents for explosives, for
decorative coatings and printing inks, light oils for use in
applications such as metal extraction, metalworking or demoulding
and industrial lubricants, and drilling fluids. The hydrocarbon
fluids can also be used as extender oils in adhesives and sealant
systems such as silicone sealants and as viscosity depressants in
plasticised polyvinyl chloride formulations and as carrier in
polymer formulation used as flocculants for example in water
treatment, mining operations or paper manufacturing and also used
as thickener for printing pastes, as plasticizers in tyre
materials. Hydrocarbon fluids may also be used as solvents in a
wide variety of other applications such as chemical reactions.
[0003] The chemical nature and composition of hydrocarbon fluids
varies considerably according to the use to which the fluid is to
be put. Important properties of hydrocarbon fluids are the
distillation range generally determined by ASTM D-86 or the ASTM
D-1160 vacuum distillation technique used for heavier materials,
flash point, density, aniline point as determined by ASTM D-611,
aromatic content, sulphur content, viscosity, colour and refractive
index.
[0004] These fluids tend to have narrow boiling point ranges as
indicated by a narrow range between Initial Boiling Point (IBP) and
Final Boiling Point (FBP) according to ASTM D-86. The Initial
Boiling Point and the Final Boiling Point will be chosen according
to the use to which the fluid is to be put. However, the use of the
narrow cuts provides the benefits of a narrow flash point and may
also prevent the emission of Volatile Organic Compounds which are
important for safety reasons. The narrow cut also brings important
fluid properties such as a better defined aniline point or solvency
power, then viscosity, and defined evaporation conditions for
systems where drying is important, and finally better defined
surface tension.
[0005] Nowadays, biodegradability is a requirement for these
specific fluids.
[0006] US2009/0014354 discloses biodegradable cuts boiling at
356-413.degree. C., and comprising mostly isoparaffins with an
amount of naphthenics of not less than 7%. The cuts originate from
biological origin.
[0007] EP2368967 discloses a solvent composition containing 5 to
30% of C.sub.10-C.sub.20 n-alkanes, and 70 to 95% of
C.sub.10-C.sub.20 iso-alkanes, by weight, said solvent composition
being produced from raw materials of biological origin. The solvent
composition has a boiling range of 180 to 340.degree. C.
[0008] WO00/20534 discloses a solvent issued from Fischer-Tropsch
synthesis and which is typically a biodegradable synthetic middle
distillate cut and has an isoparaffins to n-paraffins mass ratio of
between about 1:1 to about 12:1. The boiling range is above
80.degree. C. A preferred composition is one which has at least 30%
(mass) of the isoparaffins as mono-methyl branched.
[0009] WO2006/084285 discloses a hydrocarbon fluid composition of
synthetic origin comprising isoparaffins and a minimum initial
boiling point to maximum final boiling point at or within the range
of 110.degree. C. to 350.degree. C. and which is said to be
biodegradable. The cetane number is said to be less than 60. The
applicant is also marketing a composition ISOPAR.RTM., which
typically contains more than 20% naphthenic compounds.
[0010] US2012/0283492 discloses a process for hydrogenating a
low-sulphur feed into a fluid having a boiling range of not more
than 80.degree. C. and having an isoparaffin content of at most
about 52% by weight.
[0011] US2013/0001127 discloses a process to prepare very
low-sulphur, very low aromatic hydrocarbon fluids having a boiling
range of not more than 80.degree. C. and having an isoparaffin
content of at most 40% by weight.
[0012] US2014/0323777 discloses a process for manufacturing an
aviation fuel oil base having an isoparaffin content of 80% by
weight or more but at most 91.6%, and an aromatic content of less
than 0.1 vol %.
[0013] There is still a need for fluids with high biodegradability
and being of biological origin.
SUMMARY OF THE INVENTION
[0014] The invention provides a process for preparing a fluid
having a boiling point in the range of from 100 to 400.degree. C.
and comprising more than 95% isoparaffins and containing less than
100 ppm aromatic by weight, comprising the step of catalytically
hydrogenating a feed comprising more than 95% by weight of a
hydrodeoxygenated isomerized hydrocarbon biomass feedstock, at a
temperature from 80 to 180.degree. C., at a pressure from 50 to 160
bars, a liquid hourly space velocity of 0.2 to 5 hr.sup.-1 and an
hydrogen treat rate up to 200 Nm.sup.3/ton of feed.
[0015] According to an embodiment, the hydrogenation conditions of
the process are the following: [0016] Pressure: 80 to 150 bars, and
preferably 90 to 120 bars; [0017] Temperature: 120 to 160.degree.
C. and preferably 150 to 160.degree. C.; [0018] Liquid hourly space
velocity (LHSV): 0.4 to 3, and preferably 0.5 to 0.8; [0019]
Hydrogen treat rate be up to 200 Nm.sup.3/ton of feed.
[0020] According to an embodiment, the feed comprises more than
98%, preferably more than 99% of a hydrodeoxygenated isomerized
hydrocarbon biomass feedstock, and more preferably consists of a
hydrodeoxygenated isomerized hydrocarbon biomass feedstock.
[0021] According to an embodiment, the biomass is a vegetable oil,
an ester thereof or a triglyceride thereof.
[0022] According to an embodiment, the feed is a NEXBTL feed.
[0023] According to an embodiment, a fractionating step is carried
out before the hydrogenating step, or after the hydrogenating step
or both; according to an embodiment, the process comprises three
hydrogenation stages, preferably in three separate reactors.
[0024] The invention also provides new hydrocarbon fluids,
hereafter "improved fluids", also referring to the fluids obtained
by the process of the invention.
[0025] The invention thus provides fluids having a boiling point in
the range of from 100 to 400.degree. C. and a boiling range below
80.degree. C., said fluid comprising more than 95% isoparaffins and
less than 3% of naphthens by weight and having a ratio of
iso-paraffins to n-paraffins of at least 12:1, a biodegradability
at 28 days of at least 60%, as measured according to the OECD 306
standard, a biocarbon content of at least 95% by weight, containing
less than 100 ppm aromatics by weight, and comprising carbon
expressed as CH.sub.3 sat less than 30%.
[0026] According to an embodiment, the fluid has a boiling point in
the range 150 to 400.degree. C., preferably from 200 to 400.degree.
C., especially 220 to 340.degree. C. and advantageously more than
250.degree. C. and up to 340.degree. C.
[0027] According to an embodiment, the fluid has a boiling range
below 80.degree. C., preferably below 60.degree. C., advantageously
between 40 and 50.degree. C.
[0028] According to an embodiment, the fluid contains less than 50
ppm aromatics, and preferably less than 20 ppm by weight.
[0029] According to an embodiment, the fluid contains less than 3%
by weight of naphthens, preferably less than 1% and advantageously
less than 50 ppm by weight.
[0030] According to an embodiment, the fluid contains less than 5
ppm, even less than 3 ppm and preferably less than 0.5 ppm
sulphur.
[0031] According to an embodiment, the fluid comprises more than
98% isoparaffins by weight.
[0032] According to an embodiment, the fluid has a ratio of
iso-paraffins to n-paraffins of at least 12:1, preferably at least
15:1, more preferably at least 20:1.
[0033] According to an embodiment, the fluid comprises more than
95% by weight, of molecules with from 14 to 18 carbon atoms as
isoparaffins, preferably comprises by weight, from 60 to 95%, more
preferably 80 to 98%, of isoparaffins selected from the group
consisting of C15 isoparaffins, C16 isoparaffins, C17 isoparaffins,
C18 isoparaffins and mixtures of two or more thereof.
[0034] According to an embodiment, the fluid comprises: [0035] C15
isoparaffins and C16 isoparaffins in a combined amount of 80 to
98%; or [0036] C16 isoparaffins, C17 isoparaffins and C18
isoparaffins in a combined amount of 80 to 98%; or [0037] C17
isoparaffins and C18 isoparaffins in a combined amount of 80 to
98%.
[0038] According to an embodiment, the fluid exhibits one or more,
preferably all of the following features: [0039] the fluid
comprises carbon expressed as Cquat less than 3%, preferably less
than 1% and more preferably about 0%; [0040] the fluid comprises
carbon expressed as CH sat less than 20%, preferably less than 18%
and more preferably less than 15%; [0041] the fluid comprises
carbon expressed as CH.sub.2 sat more than 40%, preferably more
than 50% and more preferably more than 60%; [0042] the fluid
comprises carbon expressed as CH.sub.3 sat less than 30%,
preferably less than 28% and more preferably less than 25%; [0043]
the fluid comprises carbon expressed as CH.sub.3 long chain less
than 20%, preferably less than 18% and more preferably less than
15%; [0044] the fluid comprises carbon expressed as CH.sub.3 short
chain less than 15%, preferably less than 10% and more preferably
less than 9%.
[0045] According to an embodiment, the fluid has a biodegradability
at 28 days of at least 60%, preferably at least 70%, more
preferably at least 75% and advantageously at least 80%, as
measured according to the OECD 306 standard.
[0046] According to an embodiment, the fluid has a biocarbon
content of at least 95%, preferably at least 97%, more preferably
at least 98%, and even more preferably about 100%.
DESCRIPTION OF EMBODIMENTS OF THE INVENTION
[0047] The feedstock will first be disclosed, then the
hydrogenation step and the associated fractionating step, and
finally the improved fluids.
Feedstock.
[0048] The feedstock or simply feed is a feed which is the result
of a process of hydrodeoxygenation followed by isomerization,
hereafter "HDO/ISO", as practiced on a biomass.
[0049] This HDO/ISO process is applied on biological raw materials,
the biomass, selected from the group consisting of vegetable oils,
animal fats, fish oils, and mixtures thereof, preferably vegetable
oils. Suitable vegetable raw materials include rapeseed oil, canola
oil, colza oil, tall oil, sunflower oil, soybean oil, hemp oil,
olive oil, linenseed oil, mustard oil, palm oil, arachis oil,
castor oil, coconut oil, animal fats such as suet, tallow, blubber,
recycled alimentary fats, starting materials produced by genetic
engineering, and biological starting materials produced by microbes
such as algae and bacteria. Condensation products, esters, or other
derivatives obtained from biological raw materials may also be used
as starting materials. An especially preferred vegetable raw
material is an ester or triglyceride derivative. This material is
submitted to an hydrodeoxygenation (HDO) step for decomposing the
structure of the biological ester or triglyceride constituent, and
for removing oxygen, phosphorus and sulfur (part of) compounds,
concurrently hydrogenating the olefinic bonds, followed by
isomerization of the product thus obtained, thus branching the
hydrocarbon chain and improving the low temperature properties of
the thus-obtained feedstock.
[0050] In the HDO step, hydrogen gas and the biological constituent
are passed to the HDO catalyst bed either in countercurrent or
concurrent manner. In the HDO step, the pressure and the
temperature range typically between 20 and 150 bar, and between 200
and 500.degree. C., respectively. In the HDO step, known
hydrodeoxygenation catalysts may be used. Prior to the HDO step,
the biological raw material may optionally be subjected to
prehydrogenation under milder conditions to avoid side reactions of
the double bonds. After the HDO step, the product is passed to the
isomerization step where hydrogen gas and the biological
constituent to be hydrogenated, and optionally a n-paraffin
mixture, are passed to the isomerization catalyst bed either in
concurrent or countercurrent manner. In the isomerization step, the
pressure and the temperature range between typically 20 and 150
bar, and between 200 and 500.degree. C., respectively. In the
isomerization step, isomerization catalysts known as such may be
typically used.
[0051] Secondary process steps can also be present (such as
intermediate pooling, scavenging traps, and the like).
[0052] The product issued from the HDO/ISO steps may for instance
be fractionated to give the desired fractions.
[0053] Various HDO/ISO processes are disclosed in the literature.
WO2014/033762 discloses a process which comprises a
pre-hydrogenation step, a hydrodeoxygenation step (HDO) and an
isomerization step which operates using the countercurrent flow
principle. EP1728844 describes a process for the production of
hydrocarbon components from mixtures of a vegetable or animal
origin. The process comprises a pretreatment step of the mixture of
a vegetable origin for removing contaminants, such as, for example,
alkaline metal salts, followed by a hydrodeoxygenation (HDO) step
and an isomerization step. EP2084245 describes a process for the
production of a hydrocarbon mixture that can be used as diesel fuel
or diesel component by the hydrodeoxygenation of a mixture of a
biological origin containing fatty acid esters possibly with
aliquots of free fatty acids, such as for example vegetable oils
such as sunflower oil, rape oil, canola oil, palm oil, or fatty
oils contained in the pulp of pine trees (tall oil), followed by
hydroisomerization on specific catalysts. EP2368967 discloses such
a process and the thus-obtained product.
[0054] Company Neste Oy has developed specific HDO/ISO processes,
and is currently marketing products thus obtained, under the
tradename NexBTL.RTM. (diesel, aviation fuel, naphtha, isoalkane).
This NexBTL.RTM. is an appropriate feed for use in the present
invention. The NEXBTL feed is further described at
http://en.wikipedia.org/wiki/NEXBTL and/or at the neste oy
website.
[0055] Feedstocks typically contain less than 15 ppm of sulphur,
preferably less than 8 ppm and more preferably less than 5 ppm,
especially less than 1 ppm, as measured according to EN ISO 20846.
Typically the feedstocks will comprise no sulphur as being
biosourced products.
[0056] Before entering the hydrogenation unit, a pre-fractionation
step can take place. Having a more narrow boiling range entering
the unit allows having a more narrow boiling range at the outlet.
Indeed typical boiling ranges of pre-fractionated cuts are 220 to
330.degree. C. while cuts without a pre-fractionating step
typically have a boiling range from 150.degree. C. to 360.degree.
C.
Hydrogenation Step.
[0057] The feedstock issued from HDO/ISO is then hydrogenated. The
feedstock can optionally be pre-fractionated.
[0058] Hydrogen that is used in the hydrogenation unit is typically
a high purity hydrogen, e.g. with a purity of more than 99%, albeit
other grades can be used.
[0059] Hydrogenation takes place in one or more reactors. The
reactor can comprise one or more catalytic beds. Catalytic beds are
usually fixed beds.
[0060] Hydrogenation takes place using a catalyst. Typical
hydrogenation catalysts include but are not limited to: nickel,
platinum, palladium, rhenium, rhodium, nickel tungstate, nickel
molybdenum, molybdenum, cobalt molybdenate, nickel molybdenate on
silica and/or alumina carriers or zeolites. A preferred catalyst is
Ni-based and is supported on an alumina carrier, having a specific
surface area varying between 100 and 200 m.sup.2/g of catalyst.
[0061] The hydrogenation conditions are typically the following:
[0062] Pressure: 50 to 160 bars, preferably 80 to 150 bars, and
most preferably 90 to 120 bars; [0063] Temperature: 80 to
180.degree. C., preferably 120 to 160.degree. C. and most
preferably 150 to 160.degree. C.; [0064] Liquid hourly space
velocity (LHSV): 0.2 to 5 hr.sup.-1, preferably 0.4 to 3, and most
preferably 0.5 to 0.8; [0065] Hydrogen treat rate: adapted to the
above conditions, which can be up to 200 Nm.sup.3/ton of feed.
[0066] The temperature in the reactors can be typically about
150-160.degree. C. and the pressure can be typically about 100 bars
while the liquid hourly space velocity can be typically about
0.6h.sup.-1 and the treat rate is adapted, depending on the feed
quality and the first process parameters.
[0067] The hydrogenation process of the invention can be carried
out in several stages. There can be two or three stages, preferably
three stages, preferably in three separate reactors. The first
stage will operate the sulphur trapping, hydrogenation of
substantially all unsaturated compounds, and up to about 90% of
hydrogenation of aromatics. The flow exiting from the first reactor
contains substantially no sulphur. In the second stage the
hydrogenation of the aromatics continues, and up to 99% of
aromatics are hydrogenated. The third stage is a finishing stage,
allowing an aromatic content as low as 100 ppm by weight or even
less such as below 50 ppm, more preferably less than 20 ppm, even
for high boiling products.
[0068] The catalysts can be present in varying or substantially
equal amounts in each reactor, e.g. for three reactors according to
weight amounts of 0.05-0.5/0.10-0.70/0.25-0.85, preferably
0.07-0.25/0.15-0.35/0.4-0.78 and most preferably
0.10-0.20/0.20-0.32/0.48-0.70.
[0069] It is also possible to have one or two hydrogenation
reactors instead of three.
[0070] It is also possible that the first reactor be made of twin
reactors operated alternatively in a swing mode. This may be useful
for catalyst charging and discharging: since the first reactor
comprises the catalyst that is poisoned first (substantially all
the sulphur is trapped in and/or on the catalyst) it should be
changed often.
[0071] One reactor can be used, in which two, three or more
catalytic beds are installed.
[0072] It may be necessary to insert quenches on the recycle to
cool effluents between the reactors or catalytic beds to control
reaction temperatures and consequently hydrothermal equilibrium of
the hydrogenation reaction. In a preferred embodiment, there is no
such intermediate cooling or quenching.
[0073] In case the process makes use of 2 or 3 reactors, the first
reactor will act as a sulphur trap. This first reactor will thus
trap substantially all the sulphur. The catalyst will thus be
saturated very quickly and may be renewed from time to time. When
regeneration or rejuvenation is not possible for such saturated
catalyst the first reactor is considered as a sacrificial reactor
which size and catalyst content both depend on the catalyst renewal
frequency.
[0074] In an embodiment the resulting product and/or separated gas
is/are at least partly recycled to the inlet of the hydrogenation
stages. This dilution helps, if this were to be needed, maintaining
the exothermicity of the reaction within controlled limits,
especially at the first stage. Recycling also allows heat-exchange
before the reaction and also a better control of the
temperature.
[0075] The stream exiting the hydrogenation unit contains the
hydrogenated product and hydrogen. Flash separators are used to
separate effluents into gas, mainly remaining hydrogen, and
liquids, mainly hydrogenated hydrocarbons. The process can be
carried out using three flash separators, one of high pressure, one
of medium pressure, and one of low pressure, very close to
atmospheric pressure.
[0076] The hydrogen gas that is collected on top of the flash
separators can be recycled to the inlet of the hydrogenation unit
or at different levels in the hydrogenation units between the
reactors.
[0077] Because the final separated product is at about atmospheric
pressure, it is possible to feed directly the fractionation stage,
which is preferably carried out under vacuum pressure that is at
about between 10 to 50 mbars, preferably about 30 mbars.
[0078] The fractionation stage can be operated such that various
hydrocarbon fluids can be withdrawn simultaneously from the
fractionation column, and the boiling range of which can be
predetermined.
[0079] Therefore, fractionation can take place before
hydrogenation, after hydrogenation, or both.
[0080] The hydrogenation reactors, the separators and the
fractionation unit can thus be connected directly, without having
to use intermediate tanks. By adapting the feed, especially the
initial and final boiling points of the feed, it is possible to
produce directly, without intermediate storage tanks, the final
products with the desired initial and final boiling points.
Moreover, this integration of hydrogenation and fractionation
allows an optimized thermal integration with reduced number of
equipment and energy savings.
Fluids of the Invention.
[0081] The fluids of the invention, hereafter referred to simply as
"the improved fluids" possess outstanding properties, in terms of
aniline point or solvency power, molecular weight, vapour pressure,
viscosity, defined evaporation conditions for systems where drying
is important, and defined surface tension.
[0082] The improved fluids are primarily isoparaffinic and contain
more than 95% isoparaffins, preferably more than 98%.
[0083] The improved fluids typically contain less than 3% by weight
of naphthens, preferably less than 1% and advantageously less than
50 ppm by weight.
[0084] The improved fluids typically have a ratio of iso-paraffins
to n-paraffins of at least preferably at least 12:1, more
preferably at least 15:1, more preferably more than 20:1.
[0085] Typically, the improved fluids comprise carbon atoms number
from 6 to 30, preferably 8 to 24 and most preferably from 9 to 20
carbon atoms. The fluids especially comprise a majority, i.e. more
than 90% by weight, of molecules with from 14 to 18 carbon atoms as
isoparaffins. Preferred improved fluids are those comprising by
weight, from 60 to 95%, preferably 80 to 98%, of isoparaffins
selected from the group consisting of C15 isoparaffins, C16
isoparaffins, C17 isoparaffins, C18 isoparaffins and mixtures of
two or more thereof.
[0086] Preferred improved fluids comprise: [0087] C15 isoparaffins
and C16 isoparaffins in a combined amount of 80 to 98%; or [0088]
C16 isoparaffins, C17 isoparaffins and C18 isoparaffins in a
combined amount of 80 to 98%; or [0089] C17 isoparaffins and C18
isoparaffins in a combined amount of 80 to 98%.
[0090] Examples of preferred improved fluids are those comprising:
[0091] from 30 to 70% of C15 isoparaffins and from 30 to 70% C16
isoparaffins, preferably from 40 to 60% of C15 isoparaffins and
from 35 to 55% C16 isoparaffins; [0092] from 5 to 25% of C15
isoparaffins, from 30 to 70% C16 isoparaffins and from 10 to 40% of
C17 isoparaffins, preferably from 8 to 15% of C15 isoparaffins,
from 40 to 60% C16 isoparaffins and from 15 to 25% of C17
isoparaffins; [0093] from 5 to 30% of C17 isoparaffins and from 70
to 95% C18 isoparaffins, preferably from 10 to 25% of C17
isoparaffins and from 70 to 90% C18 isoparaffins.
[0094] The improved fluids exhibit a specific branching
distribution.
[0095] Branching rates of isoparaffins as well as carbon
distribution is determined using the RMN method (as well as GC-MS)
and determination of each type of carbon (with no hydrogen, with
one, two or three hydrogens). C quat sat represents the saturated
quaternary carbon, CH sat represents the saturated carbon with one
hydrogen, CH.sub.2 sat represents the saturated carbon with two
hydrogens, CH.sub.3 sat represents the saturated carbon with three
hydrogens, CH.sub.3 long chain and CH.sub.3 short chain represent
the CH.sub.3 group on a long chain and a short chain, respectively
where the short chain is one methyl group only and a long chain is
a chain having at least two carbons. The sum of CH.sub.3 long chain
and CH.sub.3 short chain is CH.sub.3 sat.
[0096] The improved fluids typically comprise carbon expressed as
Cquat less than 3%, preferably less than 1% and more preferably
about 0%.
[0097] The improved fluids typically comprise carbon expressed as
CH sat less than 20%, preferably less than 18% and more preferably
less than 15%.
[0098] The improved fluids typically comprise carbon expressed as
CH.sub.2 sat more than 40%, preferably more than 50% and more
preferably more than 60%.
[0099] The improved fluids typically comprise carbon expressed as
CH.sub.3 sat less than 30%, preferably less than 28% and more
preferably less than 25%.
[0100] The improved fluids typically comprise carbon expressed as
CH.sub.3 long chain less than 20%, preferably less than 18% and
more preferably less than 15%.
[0101] The improved fluids typically comprise carbon expressed as
CH.sub.3 short chain less than 15%, preferably less than 10% and
more preferably less than 9%.
[0102] The improved fluids have a boiling range from 100 to
400.degree. C. and also exhibit an enhanced safety, due to the very
low aromatics content.
[0103] The improved fluids typically contain less than 100 ppm,
more preferably less than 50 ppm, advantageously less than 20 ppm
aromatics (measured using a UV method). This makes them suitable
for use in crop protection fluids. This is especially useful for
high temperature boiling products, typically products boiling in
the range 300-400.degree. C., preferably 320-380.degree. C.
[0104] The boiling range of the improved fluids is preferably not
more than 80.degree. C., preferably not more than 70.degree. C.,
more preferably not more than 60.degree. C., advantageously between
40 and 50.degree. C.
[0105] The improved fluids also have an extremely low sulphur
content, typically less than 5 ppm, even less than 3 ppm and
preferably less than 0.5 ppm, at a level too low to be detected by
the usual low-sulphur analyzers.
[0106] The improved fluids find various uses, including but not
limited to: as drilling fluids, in hydraulic fracturing, in mining,
in water treatments, as industrial solvents, in paints composition,
for decorative coatings, in coating fluids, in car industry, in
textile industry, in metal extraction, in explosives, in oil
dispersants, in concrete demoulding formulations, in adhesives, in
printing inks, in metal working fluids, coating fluids, rolling
oils especially for aluminum, as cutting fluids, as rolling oils,
as electric discharge machining (EDM) fluids, rust preventive,
industrial lubricants, as extender oils, in sealants such as
mastics or polymers especially with silicone, as viscosity
depressants in plasticised polyvinyl chloride formulations, in
resins, in varnishes, as phytosanitary fluid especially as crop
protection fluids, as adjuvant or excipient in vaccine
preparations, in paint compositions, especially low-odor paints, in
polymers used in water treatment, paper manufacturing or printing
pastes especially as thickener, cleaning and/or degreasing
solvents, for slurry polymerization, in food processing industry,
for food grade application, home care, heat-transfer media, shock
absorbers, insulation oils, hydraulic oils, gear oils, turbine
oils, textile oils and in transmission fluids such as automatic
transmission fluids or manual gear box formulations, and as
solvents in chemical reactions including cristallization,
extraction and fermentation.
[0107] In all this foreseen uses, the Initial Boiling Point (IBP)
to Final Boiling Point (FBP) range is selected according to the
particular use and composition. An Initial Boiling Point of more
than 250.degree. C. allows classification as free of VOC (Volatile
Organic Compound) according to the directive 2004/42/CE.
[0108] The isoparaffinic nature of the improved fluids allows for
improved low temperature properties.
[0109] The improved fluids are also useful as components in
adhesives, sealants or polymer systems such as silicone sealant,
modified silane polymers where they act as extender oils and as
viscosity depressants for polyvinyl chloride (PVC) pastes or
Plastisol formulations.
[0110] The improved fluids may also be used as new and improved
solvents, particularly as solvents for resins. The solvent-resin
composition may comprise a resin component dissolved in the fluid,
the fluid comprising 5 to 95% by total volume of the
composition.
[0111] The improved fluids may be used in place of solvents
currently used for inks, coatings and the like.
[0112] The improved fluids may also be used to dissolve resins such
as: acrylic-thermoplastic, acrylic-thermosetting, chlorinated
rubber, epoxy (either one or two part), hydrocarbon (e.g., olefins,
terpene resins, rosin esters, petroleum resins, coumarone-indene,
styrene-butadiene, styrene, methyl-styrene, vinyl-toluene,
polychloroprene, polyamide, polyvinyl chloride and isobutylene),
phenolic, polyester and alkyd, polyurethane and modified
polyurethane, silicone and modified silicone (MS polymers), urea,
and, vinyl polymers and polyvinyl acetate.
[0113] Examples of the type of specific applications for which the
improved fluids and fluid-resin blends may be used include
coatings, cleaning compositions and inks. For coatings the blend
preferably has high resin content, i.e., a resin content of 20% to
80% by volume. For inks, the blend preferably contains a lower
concentration of the resin, i.e., 5%-30% by volume.
[0114] In yet another embodiment, various pigments or additives may
be added.
[0115] The improved fluids can be used as cleaning compositions for
the removal of hydrocarbons
[0116] The improved fluids may also be used in cleaning
compositions such as for use in removing ink, more specifically in
removing ink from printing.
[0117] In the offset printing industry it is important that ink can
be removed quickly and thoroughly from the printing surface without
harming the metal or rubber components of the printing machine.
Further there is a tendency to require that the cleaning
compositions are environmentally friendly in that they contain no
or hardly any aromatic volatile organic compounds and/or halogen
containing compounds. A further trend is that the compositions
fulfil strict safety regulations. In order to fulfil the safety
regulations, it is preferred that the compositions have a flash
point of more than 62.degree. C., more preferably a flash point of
90.degree. C. or more. This makes them very safe for
transportation, storage and use. The improved fluids have been
found to give a good performance in that ink is readily removed
while these requirements are met.
[0118] The improved fluids are also useful as drilling fluids, such
as a drilling fluid which has the fluid prepared by the process of
this invention as a continuous oil phase. The improved fluids may
also be used as a penetration rate enhancer comprising a continuous
aqueous phase containing the improved fluid dispersed therein.
[0119] Fluids used for offshore or on-shore applications need to
exhibit acceptable biodegradability, human, eco-toxicity,
eco-accumulation and lack of visual sheen credentials for them to
be considered as candidate fluids for the manufacturer of drilling
fluids. In addition, fluids used in drilling uses need to possess
acceptable physical attributes. These generally include a viscosity
of less than 4.0 mm.sup.2/s at 40.degree. C., a flash value of
usually more than 90.degree. C. and, for cold weather applications,
a pour point at -40.degree. C. or lower. These properties have
typically been only attainable through the use of expensive
synthetic fluids such as hydrogenated polyalphaolefins, as well as
unsaturated internal olefins and linear alpha-olefins and esters.
The properties can now be obtained in the improved fluids.
[0120] Drilling fluids may be classified as either water-based or
oil-based, depending upon whether the continuous phase of the fluid
is mainly oil or mainly water. Water-based fluids may however
contain oil and oil-based fluids may contain water and the fluids
produced according to the process of the invention are particularly
useful as the oil phase.
[0121] Typically preferred ASTM D-86 boiling ranges for the uses of
the fluids are that of printing ink solvents (sometimes known as
distillates) have boiling ranges in the ranges of 235.degree. C. to
265.degree. C., 260.degree. C. to 290.degree. C., 280.degree. C. to
315.degree. C. and 300.degree. C. to 355.degree. C. Fluids
preferred for use as drilling fluids have boiling ranges in the
ranges of 195.degree. C. to 240.degree. C., 235.degree. C. to
265.degree. C. and 260.degree. C. to 290.degree. C. Fluids
preferred for explosives, concrete demoulding, industrial
lubricants, transmission fluids and metal working fluids have
boiling ranges in the ranges of 185.degree. C. to 215.degree. C.,
195.degree. C. to 240.degree. C., 235.degree. C. to 365.degree. C.,
260.degree. C. to 290.degree. C., 280.degree. C. to 325.degree. C.
and 300.degree. C. to 360.degree. C. Fluids preferred as extenders
for sealants have boiling ranges in the ranges of 195.degree. C. to
240.degree. C., 235.degree. C. to 265.degree. C., 260.degree. C. to
290.degree. C., 280.degree. C. to 325.degree. C. or 300.degree. C.
to 360.degree. C. Fluids preferred as viscosity depressants for
polyvinyl chloride plastisols have boiling ranges in the ranges of
185.degree. C. to 215.degree. C., 195.degree. C. to 240.degree. C.,
235.degree. C. to 265.degree. C., 260.degree. C. to 290.degree. C.,
280.degree. C. to 315.degree. C. and 300.degree. C. to 360.degree.
C.
[0122] Fluids preferred as carrier for polymeric composition used
in water treatment, mining operation or printing pastes have
boiling ranges in the ranges of 185.degree. C. to 215.degree. C.,
195.degree. C. to 240.degree. C., 235.degree. C. to 265.degree. C.,
260.degree. C. to 290.degree. C., 280.degree. C. to 315.degree. C.
and 300.degree. C. to 360.degree. C.
[0123] Fluids preferred for crop protection application have
boiling ranges in the range of 300 and 370.degree. C., such fluids
being used in combination with hydrocarbon fluids such as
isodewaxed hydrocarbons or any hydrocarbons having comparable
properties such as viscosity.
[0124] For paint compositions and cleaning applications, the most
preferred boiling ranges are in the ranges of 140 to 210.degree.
C., and 180 to 220.degree. C. Fluids showing an initial boiling
point above 250.degree. C. and a final boiling point close to
330.degree. C. or preferably close to 290.degree. C. will be
preferred for low VOC coatings formulations.
[0125] Biodegradation of an organic chemical refers to the
reduction in complexity of the chemical through metabolic activity
of microorganisms. Under aerobic conditions, microorganisms convert
organic substances into carbon dioxide, water and biomass. OECD 306
method, is available for assessing biodegradability of individual
substances in seawater. OECD Method 306 can be carried out as
either a shake flask or Closed Bottle method and the only
microorganisms added are those microorganisms in the test seawater
to which the test substance is added. In order to assess the biotic
degradation in seawater, a biodegradability test was performed
which allows the biodegradability to be measured in seawater. The
biodegradability was determined in the Closed Bottle test performed
according to the OECD 306 Test Guidelines. The biodegradability of
the improved fluids is measured according to the OECD Method
306.
[0126] The OECD Method 306 is the following:
[0127] The closed bottle method consists on dissolution of a
pre-determined amount of the test substance in the test medium in a
concentration of usually 2-10 mg/1, with one or more concentrations
being optionally used. The solution is kept in a filled closed
bottle in the dark in a constant temperature bath or enclosure
controlled within a range of 15-20.degree. C. The degradation is
followed by oxygen analyses over a 28-day period. Twenty-four
bottles are used (8 for test substance, 8 for reference compound
and 8 for sweater plus nutriment). All analyses are performed on
duplicate bottles. Four determinations of dissolved oxygen, at
least, are performed (day 0, 5, 15 and 28) using a chemical or
electrochemical method.
[0128] Results are thus expressed in % degradability at 28 days.
The improved fluids have a biodegradability at 28 days of at least
60%, as measured according to the OECD 306 standard, preferably at
least 70% by weight, more preferably at least 75% and
advantageously at least 80%.
[0129] The invention uses the products of natural origin like
starting products. The carbon of a biomaterial comes from the
photosynthesis of the plants and thus of atmospheric CO.sub.2. The
degradation (by degradation, one will understand also
combustion/incineration at the end of the lifetime) of these CO2
materials thus does not contribute to the warming since there is no
increase in the carbon emitted in the atmosphere. The assessment
CO.sub.2 of the biomaterials is thus definitely better and
contributes to reduce the print carbon of the products obtained
(only energy for manufacture is to be taken into account). On the
contrary, a fossil material of origin being also degraded out of
CO.sub.2 will contribute to the increase in the CO.sub.2 rate and
thus to climate warming. The improved fluids according to the
invention will thus have a print carbon which will be better than
that of compounds obtained starting from a fossil source.
[0130] The invention thus improves also the ecological assessment
during the manufacture of the improved fluids. The term of
"bio-carbon" indicates that carbon is of natural origin and comes
from a biomaterial, as indicated hereafter. The content of
biocarbon and the content of biomaterial are expressions indicating
the same value.
[0131] A renewable material of origin or biomaterial is an organic
material in which carbon comes from CO.sub.2 fixed recently (on a
human scale) by photosynthesis starting from the atmosphere. On
ground, this CO.sub.2 is collected or fixed by the plants. At sea,
CO.sub.2 is collected or fixed by microscopic bacteria or plants or
algae carrying out a photosynthesis. A biomaterial (carbon natural
origin 100%) presents an isotopic ratio .sup.14C/.sup.12C higher
than 10.sup.-12, typically about 1.2.times.10.sup.-12, while a
fossil material has a null ratio. Indeed, the isotope .sup.14C is
formed in the atmosphere and is then integrated by photosynthesis,
according to a scale of time of a few tens of years at the maximum.
The half-life of .sup.14C is 5730 years. Thus the materials
resulting from photosynthesis, namely the plants in a general way,
have necessarily a maximum content of isotope .sup.14C.
[0132] The determination of the content of biomaterial or content
of biocarbon is given pursuant to standards ASTM D 6866-12, method
B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04). Standard ASTM
D 6866 concerns "Determining the Biobased Content of Natural Range
Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry
Analysis", while standard ASTM D 7026 concerns "Sampling and
Reporting of Results for Determination of Biobased Content of
Materials via Carbon Isotope Analysis". The second standard
mentions the first in its first paragraph.
[0133] The first standard describes a test of measurement of the
ratio .sup.14C/.sup.12C of a sample and compares it with the ratio
.sup.14c/.sup.12C of a sample renewable reference of origin 100%,
to give a relative percentage of C of origin renewable in the
sample. The standard is based on the same concepts that the dating
with .sup.14C, but without making application of the equations of
dating. The ratio thus calculated is indicated as the "pMC"
(percent Modem Carbon). If the material to be analyzed is a mixture
of biomaterial and fossil material (without radioactive isotope),
then the value of pMC obtained is directly correlated with the
quantity of biomaterial present in the sample. The value of
reference used for the dating to .sup.14C is a value dating from
the years 1950. This year was selected because of the existence of
nuclear tests in the atmosphere which introduced great quantities
of isotopes into the atmosphere after this date. The reference 1950
corresponds to a value pMC of 100. Taking into account the
thermonuclear tests, the current value to be retained is
approximately 107.5 (what corresponds to a factor of correction of
0.93). The signature into radioactive carbon of a current plant is
thus of 107.5. A signature of 54 pMC and 99 pMC thus correspond to
a quantity of biomaterial in the sample of 50% and 93%,
respectively.
[0134] The compounds according to the invention come at least
partly from biomaterial and thus present a content of biomaterial
from at least 95%. This content is advantageously even higher, in
particular more than 98%, more preferably more than 99% and
advantageously about 100%. The compounds according to the invention
can thus be bio-carbon of 100% biosourced or on the contrary to
result from a mixture with a fossil origin. According to an
embodiment, the isotopic ratio .sup.14C/.sup.12C is between 1.15
and 1.2.times.10.sup.-12.
[0135] All percentages and ppm are by weight unless indicated to
the contrary. Singular and plural are used interchangeably to
designate the fluid(s).
[0136] The following example illustrates the invention without
limiting it.
EXAMPLE
[0137] A feedstock being a NEXBTL feedstock (isoalkane) is used in
the process of the invention. The following conditions for
hydrogenation are used:
[0138] The temperature in the reactors is about 150-160.degree. C.;
the pressure is about 100 bars and the liquid hourly space velocity
is 0.6h.sup.-1; the treat rate is adapted. The catalyst used is
nickel on alumina.
[0139] Fractionating is carried out to provide 3 fluids according
to the invention.
[0140] The resulting products have been obtained, with the
following properties.
TABLE-US-00001 Characteristic Ex. 1 Ex. 2 Ex. 3 Aromatic content
(ppm) <20 <20 <20 Sulfur content (ppm) 0.1 0.1 0.11 %
isoparaffins (w/w) 98.9 95.1 96.2 % n-paraffins (w/w) 1.1 4.9 3.8 %
naphthenic (w/w) 0 0 0 C15 (iso) 48.35 11.45 0 C16 (iso) 42.80
47.89 1.58 C17 (iso) 2.52 18.57 14.17 C18 (iso) 0.38 17.07 79.69 C
quat sat 0 0 0 CH sat 12.1 10.9 10.2 CH.sub.2 sat 64.9 67.8 70.7
CH.sub.3 sat 22.9 21.2 19.1 CH.sub.3 long chain 14.2 13.3 12
CH.sub.3 short chain 8.7 8 7.1 Biocarbon content (%) 97 97 98
Initial Boiling Point (.degree. C.) 247.0 259.5 293.6 5% point
(.degree. C.) 255.7 270.2 296.7 50% point (.degree. C.) 258.9 274.5
298.5 95% point (.degree. C.) 266.8 286.4 305.3 Dry point (.degree.
C.) 269.0 287.5 324.1 OECD biodegradability (28 days) (%) 80 83
83
[0141] These results show that the product prepared according to
the process of the invention is free of sulphur and exhibits a very
low aromatic content, and is isoparaffinic in nature. Its specific
branching distribution and ultra low aromatics content allow for
biodegradability and compliance with stringent regulations. Its
properties make it very suitable for hydrocarbon fluid applications
as special fluids.
* * * * *
References